EP0417922B1 - Erzeugung von reinem Kohlendioxid - Google Patents

Erzeugung von reinem Kohlendioxid Download PDF

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Publication number
EP0417922B1
EP0417922B1 EP90309118A EP90309118A EP0417922B1 EP 0417922 B1 EP0417922 B1 EP 0417922B1 EP 90309118 A EP90309118 A EP 90309118A EP 90309118 A EP90309118 A EP 90309118A EP 0417922 B1 EP0417922 B1 EP 0417922B1
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Prior art keywords
carbon dioxide
stream
drier
feed
waste stream
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EP90309118A
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English (en)
French (fr)
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EP0417922A1 (de
Inventor
Ramachandran Krishnamurthy
Donald L. Maclean
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Linde LLC
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BOC Group Inc
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/08—Separating gaseous impurities from gases or gaseous mixtures or from liquefied gases or liquefied gaseous mixtures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/50—Carbon dioxide
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
    • F25J3/0266—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of carbon dioxide
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2200/00—Processes or apparatus using separation by rectification
    • F25J2200/02—Processes or apparatus using separation by rectification in a single pressure main column system
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2200/00—Processes or apparatus using separation by rectification
    • F25J2200/74—Refluxing the column with at least a part of the partially condensed overhead gas
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/40—Processes or apparatus using other separation and/or other processing means using hybrid system, i.e. combining cryogenic and non-cryogenic separation techniques
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/60—Processes or apparatus using other separation and/or other processing means using adsorption on solid adsorbents, e.g. by temperature-swing adsorption [TSA] at the hot or cold end
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/60—Processes or apparatus using other separation and/or other processing means using adsorption on solid adsorbents, e.g. by temperature-swing adsorption [TSA] at the hot or cold end
    • F25J2205/66—Regenerating the adsorption vessel, e.g. kind of reactivation gas
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2210/00—Processes characterised by the type or other details of the feed stream
    • F25J2210/04—Mixing or blending of fluids with the feed stream
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2215/00—Processes characterised by the type or other details of the product stream
    • F25J2215/04—Recovery of liquid products
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2215/00—Processes characterised by the type or other details of the product stream
    • F25J2215/80—Carbon dioxide
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2220/00—Processes or apparatus involving steps for the removal of impurities
    • F25J2220/80—Separating impurities from carbon dioxide, e.g. H2O or water-soluble contaminants
    • F25J2220/82—Separating low boiling, i.e. more volatile components, e.g. He, H2, CO, Air gases, CH4
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2230/00—Processes or apparatus involving steps for increasing the pressure of gaseous process streams
    • F25J2230/30—Compression of the feed stream
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2245/00—Processes or apparatus involving steps for recycling of process streams
    • F25J2245/02—Recycle of a stream in general, e.g. a by-pass stream
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/90—External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S62/00—Refrigeration
    • Y10S62/928—Recovery of carbon dioxide

Definitions

  • This invention relates to a process for producing substantially pure carbon dioxide from a feed stream containing carbon dioxide and at least two other components.
  • the invention also relates to apparatus for freezing food with liquid carbon dioxide.
  • Carbon dioxide is conventionally obtained as a gaseous by-product from the production of ammonia or hydrogen a well as from fermentation plants.
  • the by-product generally contains at least 98% carbon dioxide. It is known to convert the gaseous by-product into pure liquid carbon dioxide by distillation at recoveries exceeding 94% by weight.
  • US -A- 4,639,257 (corresponding to GB-A-2 174 379) discloses a process for producing liquid carbon dioxide in which a membrane separator is used to separate gaseous carbon dioxide from components of a waste stream.
  • the system is said to be useful to treat low concentration feed sources by compressing the feed gas to high pressures of at least 1380 kPa (200 psia).
  • the membrane separation disclosed in US -A- 4,639,257 is limited to removing only those impurities which are significantly less permeable through the membrane than carbon dioxide, and are not suitable for the separation of impurities such as oxygen, which although slightly less permeable than carbon dioxide, are not readily separated by membrane separation systems.
  • US-A-4 072 276 relates to a method of chilling articles with a liquified gas, in which an exhaust gas including vapour vapour evolved from the liquified gas, is compressed refrigerated and returned into heat exchange relationship with the articles.
  • the present invention utilises a combination of distillation and pressure swing adsorption to separate a liquid carbon dioxide product from an exhaust gas evolved from a food freezing system that employs liquid carbon dioxide as a freezing medium.
  • the invention also provides an apparatus for freezing food using liquid carbon dioxide comprising:
  • a feed gas stream is sent via line 2 to a multistage compressor 4 and then via line 5 to a cooler 6 in which condensate water is removed and then discharged via line 8.
  • the cooled feed gas stream is sent via line 10 to a drier 12 where it is dried by an adsorbent (such as alumina) which adsorbs water vapour but not carbon dioxide.
  • an adsorbent such as alumina
  • the dried feed gas stream proceeds via line 14 to a second cooler 16 and then to a distillation column 18 via line 20.
  • a liquid reflux stream is produced by a refrigeration system including a condenser 22.
  • Substantially pure liquid carbon dioxide is removed from the bottom of the column 18 via line 24.
  • a gaseous waste product containing a predominant amount of carbon dioxide and impurities such as nitrogen gas is separated and removed as an overhead stream via line 26 to a heat exchanger 28 wherein it is heated.
  • the gas stream is sent via line 30 to a heater 32.
  • line 14 may be made to run in countercurrent relationship to line 26 within the heat exchanger 28 thereby eliminating the separate cooler 16.
  • the gas stream is heated in the heater 32 to a temperature sufficient to regenerate the drier 12 (which it enters via line 34) so as to dry the cooled feed stream coming from the cooler 6 via line 10. Thereafter, the waste stream including all of the carbon dioxide contained therein is vented to the atmosphere via line 36. Because the waste stream contains a major portion of carbon dioxide, the conventional system of Figure 1 is suited only for feeds containing a high carbon dioxide concentration.
  • FIG. 2 there is shown a plot of carbon dioxide recovery versus carbon dioxide feed concentration under varying pressure and temperature conditions in the distillation column. It should be noted that all concentrations of the carbon dioxide in gas streams including the feed are expressed as a percentage by volume and all carbon dioxide recoveries are expressed as a percentage by weight.
  • Plots 1 to 4 of Figure 2 represent the recoveries obtained using the above-described conventional system.
  • the column by operating the column at 1792 kPa (260 psia) and a temperature of -32°C (-25°F) (plot 1), it is possible to obtain a 94% weight recovery of carbon dioxide only when the feed concentration is about 98% by volume.
  • a pressure of 2344 kPa (340 psia); a temperature of -46°C (-50°F) a 94% weight recovery of carbon dioxide can be obtained only when the feed concentration is at least 89% by volume.
  • the conventional distillation system is useful only for high carbon dioxide concentration feed systems.
  • a feed gas stream is sent via a line 100 to a compressor 102 and then the compressed gas stream is passed via a line 104 to a cooler 106 where the stream is cooled to condense water therefrom.
  • the condensate is removed via a line 107.
  • the gas stream is then sent via line 108 to a drier 110.
  • Heat to regenerate the drier 110 is at least partially supplied by all or part of a waste stream from a pressure swing adsorber apparatus as described hereinafter so as to dry the gas stream.
  • the dried feed stream flows via line 112 to a cooler 114 and the cooled stream flows into a distillation column 116 via the line 115, which column 116 houses the condenser 119 of a refrigeration unit to obtain a liquid reflux, for separating the feed into a pure liquid carbon dioxide product and a waste stream containing a significant amount of carbon dioxide.
  • the liquid carbon dioxide product is removed from the bottom of the distillation column 116 via a line 117.
  • the waste stream leaves the distillation column 116 via a line 118 and is warmed from a column temperature of, for example, about -37°C(-35°F) to about 32°C (90°F) in a heat exchanger 120.
  • the heat exchanger 120 and the cooler 114 can be integrated so that all or part of the cooling energy required for cooling the feed can be provided by the cold stream leaving the distillation column 116 which requires warming.
  • the heated waste stream obtained from the heat exchanger 120 is sent via a line 122 to a pressure swing adsorber 124.
  • the pressure swing adsorber (PSA) 124 contains a molecular sieve or activated carbon adsorbent for separating carbon dioxide from the other gases in the waste stream.
  • a typical example of the molecular sieve is zeolite 13X manufactured by Laporte Industries, Inc.
  • PSA is a well-known apparatus for separating the components of a mixture of gases as a result of the difference in the degree of adsorption among them on a particulate adsorbent retained in a stationary bed.
  • two or more such beds are operated in a cyclic process comprising adsorption under pressure and desorption under comparatively lower pressure or vacuum. The desired component or components of the gas mixture can be obtained during either of these stages.
  • the cycle may contain other steps in addition to the fundamental steps of adsorption and regeneration, and it is commonplace where such a unit contains more than two adsorbent beds to have N beds cycled (360/N)° out of phase, thereby providing a pseudo-continuous flow of desired product.
  • the waste stream is separated in the PSA 124 into a carbon dioxide-enriched recycle stream (obtained during desorption) which is sent via a line 126 to a vacuum pump 127, and a waste stream 130 (comprising the non-adsorbed gas and produced during adsorption) containing a relatively small amount of carbon dioxide.
  • the carbon dioxide-rich stream is sent from the pump 127 via a line 128 to join the feed gas in line 100.
  • the waste stream is released from the PSA 124 under pressure via a line 130 to a pressure reducing valve 132 where the pressure is reduced before the waste stream enters the drier 110. All or a portion of the reduced pressure stream then passes through line 134 and enters a heater 136 where the stream is heated to provide regeneration for the drier 110 via a line 138.
  • the amount of reduced pressure waste stream used to regenerate the drier 110 may be controlled by providing a pathway for the flow of at least a portion of the waste stream outside of the drier 110.
  • all or part of the waste stream can by-pass the drier 110 via a line 140 before being reunited with the waste stream leaving the drier 110 via a line 141.
  • all or a portion of the carbon dioxide-enriched stream from the line 138 is used to regenerate the drier 110 instead of the waste stream from the PSA apparatus 124. More specifically, the carbon dioxide stream from the line 128 is sent to the heater 136 and via the line 138 to the drier 110. Any by-pass carbon dioxide is sent through the line 140. The carbon dioxide stream leaves the drier 110 and is cooled in a cooler 142 before returning to the feed line 100 via the line 144. In the embodiment described in Figure 4, the waste stream which leaves the PSA 124 via the line 130 passes through the pressure reducing valve 132 before being discharged from the system.
  • the process of the present invention can consistently exceed recoveries of 94% by weight of carbon dioxide for low concentration feeds containing as low as 35% carbon dioxide.
  • waste streams from highly contaminated carbon dioxide containing sources such as commercial food freezing systems using liquid carbon dioxide for freezing food can be treated to recover highly pure liquid carbon dioxide which can be recycled to the food freezer and thereby reduce the cost of commercial refrigeration.
  • the preferred embodiment of the process according to the present invention is to operate at high recoveries exceeding 94% by weight for any feed stream having a concentration of about 35% to about 98% by volume carbon dioxide, though, if desired, the process can operate at lower than 94% by weight carbon dioxide recoveries.
  • FIG 5 there is shown an overall system wherein the apparatus shown in Figure 3 is applied to recover liquid carbon dioxide from the vent gas of food freezers employing liquid carbon dioxide for food freezing.
  • Food such as meat, e.g. chicken, enters a food freezer 200 via a line 201 such as a conveyer belt.
  • the food passes through the freezer 200 and is sprayed with liquid carbon dioxide entering the food freezer 200 via a line 204.
  • the frozen food leaves the freezer via an outlet 202 for packaging.
  • the carbon dioxide gas is exhausted from the freezer via a line 205 at regular time intervals when necessary in order to maintain the freezer at the desired temperature.
  • the air is vented with the waste carbon dioxide via a line 205.
  • pressurised air is sent into the line 205 via a line 206.
  • the pressurised air may be generated by a fan or similar device.
  • the pressurised air also serves to warm the air/carbon dioxide mixture in the line 205.
  • the resulting vent gas is sent via the line 205 to a control valve 207 which is provided to maintain the flow of the vent gas to the carbon dioxide recovery system.
  • vent gas is sent to a gas holder 208 which serves to collect the vent gas and to provide a uniform recycle feed stream via a line 209.
  • This feed stream enters the carbon dioxide recovery system 210 previously described in connection with Figure 3.
  • the liquid carbon dioxide obtained from the system via a line 212 is combined with make-up liquid carbon dioxide from a line 213 and sent to the freezer 200 via the line 204.
  • the make-up liquid carbon dioxide is needed to compensate for the carbon dioxide losses resulting from leakage through the food inlet 201 and the food outlet 202 of the freezer system and the carbon dioxide which may be lost in the recovery system.
  • the compressed feed was cooled to 35°C (95°F) and then forwarded to a drier where the water content was reduced from saturation to an amount given a dew point of -62°C (-80°F).
  • the dried feed was then cooled to -18°C (0°F) and sent to the distillation column. Pure liquid carbon dioxide was obtained from the bottom of the column at a flow rate of 126.1 lb mol/hr.
  • a waste stream (96.9 lb mol/hr) containing 65.4% carbon dioxide, 27.28% nitrogen and 7.25% oxygen was discharged as an overhead stream from the column at a temperature of -37°C (-35°F) and a pressure of 1764.9 kPa (256.0 psia) and sent to a heat exchanger for warming to 32°C (90°F).
  • a portion of the waste stream (17.9 lb mol/hr) was then sent to a heater to raise the temperature to 150°C (300°F) to provide for the regeneration of the drier.
  • the remainder of waste stream (79.0 lb mol/hr) by-passed the heater and joined the other portion of the waste stream.
  • the combined waste stream was vented to the atmosphere at the rate of 96.9 lb mol/hr. Almost two thirds of the discharged waste gas was carbon dioxide.
  • the feed entered the distillation column at the same temperature and pressure conditions as in the comparative example and produced pure liquid carbon dioxide at a flow rate of 186.0 lb mol/hr.
  • the waste stream (98.9 lb mol/hr) containing the same composition as the comparative example was fed to the PSA to separate the carbon dioxide from the contaminants.
  • the carbon dioxide-enriched stream leaving the PSA contained 98.9% carbon dioxide at a flow rate of 61.8 lb mol/hr which was recycled to the feed.
  • the waste stream leaving the PSA at the rate of 37.0 lb mol/hr contained only 8.82% carbon dioxide with the balance being nitrogen and oxygen.
  • One portion of the stream (22.8 lb mol/hr) was used to regenerate the drier while the balance (14.2 lb mol/hr) by-passed the drier and combined with the other portion of the waste stream for venting.
  • the flow rate of the liquid carbon dioxide leaving the distillation column was 205.9 lb mol/hr while a waste stream containing the same composition as described in Example 1 was fed to the PSA.
  • the resulting carbon dioxide-enriched stream contained 98.9% carbon dioxide and was recycled at the rate of 29.0 lb mol/hr. A portion of this stream (20.2 lb mol/hr) was used to regenerate the drier.
  • the waste stream contained 8.82% carbon dioxide.
  • the use of the carbon dioxide-enriched stream is desirable when the initial feed concentration of carbon dioxide is high (eg 93% by volume). This is because the waste stream discharged from the PSA is inadequate to regenerate the drier.
  • the compressed feed was cooled to 35°C (95°F) and then forwarded to a drier where the water content was reduced from saturation to an amount giving a dew point of 62°C (-80°F).
  • the dried feed was then cooled to -18°C (0°F) and sent to the distillation column. Pure liquid carbon dioxide was obtained from the bottom of the column at a flow rate of 73.3 lb mol/hr.
  • a waste stream (247.0 lb mol/hr) containing 40.1% carbon dioxide, 47.3% nitrogen and 12.6% oxygen was discharged as an overhead from the column at a temperature of -50°F and a pressure of 340.0 psia and sent to a heat exchanger for warming to 32°C (90°F).
  • the waste stream was then fed to the PSA wherein the carbon dioxide was separated from the contaminants.
  • the carbon dioxide-enriched stream leaving the PSA contained 97% carbon dioxide at a flow rate of 97.1 lb mol/hr which was recycled to the feed.
  • the waste stream leaving the PSA at the rate of 149.9 lb mol/hr contained only 3.3% carbon dioxide with the balance being nitrogen and oxygen.
  • One portion of the stream (25.7 lb mol/hr) was used to regenerate the drier while the balance (124.2 lb mol/hr) by-passed the drier and combined with the other portion of the waste stream for venting.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Separation Of Gases By Adsorption (AREA)

Claims (11)

  1. Ein Verfahren zum Erzeugen von im wesentlichen reinem Kohlendioxid aus einem Kohlendioxidspeisestrom, das Kohlendioxid und zumindest zwei andere Komponenten enthält, das die Schritte umfaßt, daß:
    a` die Kohlendioxidspeisung destilliert wird, um dadurch ein im wesentlichen reines flüssiges Kohlendioxidprodukt und einen ersten Abgasstrom zu bilden, der Kohlendioxid enthält;
    b. der erste Abgasstrom in einen kohlendioxidangereicherten Strom und einen kohlendioxidabgereicherten zweiten Abgasstrom getrennt wird; und
    c. der kohlendioxidangereicherte Strom zu dem Destillationsschritt rezykliert wird;
    dadurch gekennzeichnet, daß die zwei anderen Komponenten Sauerstoff und Stickstoff sind, der Speisestrom ein gasförmiges Nebenprodukt ist, das aus einem Kühlsystem erhalten wird, welches flüssiges Kohlendioxid verwendet, um Nahrungsmittel zu gefrieren, und der erste Abgasstrom durch Druckschwungadsorption getrennt wird.
  2. Ein Verfahren nach Anspruch 1, das weiter die Schritte umfaßt, daß der Kohlendioxidspeisestrom komprimiert wird; der komprimierte Speisestrom getrocknet wird; und der getrocknete Speisestrom stromaufwärts seiner Destillation gekühlt wird.
  3. Ein Verfahren nach Anspruch 2, das weiter den Schritt umfaßt, daß zumindest ein Teil des zweiten Abgasstroms zu einem Trockner durchgeführt wird, um Wärme für den Trockner Vorzusehen, und danach der zweite Abgasstrom aus dem Trocknermittel abgelassen wird.
  4. Ein Verfahren nach Anspruch 2, das weiter den Schritt umfaßt, daß zumindest ein Teil des kohlendioxidangereicherten Stromes zu einem Trockner durchgeführt wird, um Wärme für das Trocknermittel vorzusehen und danach der kohlendioxidangereicherte Strom an den Destillationsschritt geführt wird.
  5. Ein Verfahren nach einem der Ansprüche 1 bis 4, worin die Konzentration von Kohlendioxid in der Speisung von 35 bis 98 Volumen-% beträgt.
  6. Ein Verfahren nach einem der Vorhergehenden Ansprüche, worin die Trennung durch Druckschwungadsorption zumindest zwei Betten verwendet, wobei die Betten ein Molekularsieb oder aktivierten Kohlenstoff als ein Adsorbens enthalten.
  7. Ein Verfahren nach einem der vorhergehenden Ansprüche, worin der Schritt des Destillierens der Kohlendioxidspeisung bei einer Temperatur Von -32°C bis -46°C (-25°F bis -50°F) und einem Druck von 1790 kPa bis 2340 kPa (260 psia bis 340 psia) durchgeführt wird.
  8. Vorrichtung zum Gefrieren Von Nahrungsmitteln mit flüssigem Kohlendioxid mit:
    a. einem Gefrierer (200), der dazu angepaßt ist, Nahrungsmittel zu frieren, indem flüssiges Kohlendioxid verwendet wird;
    b. einem Mittel (201 bzw. 202) zum jeweiligen Fördern von nicht gefrorenem Nahrungsmittel an den Gafrierer (200) und zum Entziehen von gefrorenem Nahrungsmittel aus dem Gefrierer (200);
    c. einem Auslaß (205) von dem Gefrierer für die Abgabe einer gasförmigen Mischung, die Kohlendioxid, Stickstoff und Sauerstoff aus dem Gefrierer (200) enthält;
    dadurch gekennzeichnet, daß die Vorrichtung zusätzlich umfaßt:
    d. eine Destillationssäule (116) zum Trennen der gasförmigen Mischung mit einem Einlaß (115) für die gasförmige Mischung und einem Auslaß (117) für im vesentlichen reines flüssiges Kohlendioxidprodukt und einem anderen Auslaß (118) für einen ersten Abgasstrom, der Kohlendioxid enthält;
    e. einen Druckschwungadsorptionstrenner (124), der dazu angepaßt ist, den ersten Abgasstrom zu einem kohlendioxidangereicherten Strom und einem kohlendioxidabgereicherten zweiten Abgasstrom zu trennen; und
    f. ein Mittel (127, 128) zum Rezyklieren des kohlendioxidangereicherten Stromes zu der Destillationssäule (116).
  9. Vorrichtung nach Anspruch 8, die weiter umfaßt einen Kompressor (102) zum Komprimieren der gasförmigen Mischung, einen Trockner (110) zum Trocknen der komprimierten gasförmigen Mischung und ein Mittel (114) Zum Kühlen dar getrockneten gasförmigen Mischung.
  10. Vorrichtung nach Anspruch 9, die weiter umfaßt: Mittel (130, 132, 134, 136, 138) zum Durchführen zumindest eines Teils des zweiten Abgasstromes an den Trockner (110), um Wärme am Trockner (110) vorzusehen.
  11. Vorrichtung nach Anspruch 9, die weiter umfaßt: Mittel (126, 128, 136, 138) zum Durchführen zumindest eines Teils des kohlendioxidangereicherten Stromes zu dem Trockner (110), um Wärme am Trockner vorzusehen, und einem Mittel (142, 144) zum Durchführen des kohlendioxidangereicherten Stromes aus dem Trocknungsmittel an die Destillationssäule (116).
EP90309118A 1989-08-21 1990-08-20 Erzeugung von reinem Kohlendioxid Expired - Lifetime EP0417922B1 (de)

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US07/396,584 US4952223A (en) 1989-08-21 1989-08-21 Method and apparatus of producing carbon dioxide in high yields from low concentration carbon dioxide feeds
US396584 1989-08-21

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KR910004466A (ko) 1991-03-28
US4969338A (en) 1990-11-13
AU626711B2 (en) 1992-08-06
DE69009127D1 (de) 1994-06-30
JPH03165809A (ja) 1991-07-17
EP0417922A1 (de) 1991-03-20
AU6103090A (en) 1991-02-21
JP3140761B2 (ja) 2001-03-05
DE69009127T2 (de) 1994-09-01
US4952223A (en) 1990-08-28

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